Transparentizing to obtain patterned cotton textiles employing resists of pigment containing aqueous oleaginous emulsions



Patented Sept. 23, 1952 RESISTS OF PIGMENT CON TAINING AQUE- OLEAGINOUS EMULSIONS Heinz Ginlzel, Dornbirn, Vorarlberg, Austria No Drawing. Application July 11, 1947, Serial No.

' 760,513; In-Germany October 18, 1941:

Section 1, 1' 1 15'1'1cLaw 690, August 8, 1946 Patent expires October 18, 1961 This invention relates to improvements in or relating to figured textiles. fj

For obtaining figured effects on fabricsby' printing with pigments, thev pigments are fixed on thesurface of the fabricsby the aid of bindings materials." Albuminesiel .g. albumine, ca-

' "7 Claims.- 8-

thread is "visible within the pigmented area.

Another object of the invention is to provide a process for producing textile goods having the seine, coagulated or hardened gelatin'e), natural and artificia1 resins, and; derivatives ofcellulo se have been used as binding materials. These binding substances however are not removable by washing. The, same binding materials are used, when fabrics, printed with pigments, are treated, before and/or after the printing, once o several times with lye and/or acids or other hydrolysing agents to improv the sameand especially to impart thereto a transparent appearance ,Thus it is known, that completely stiffened figured cfqualities mentioned above. Other objects of the invention will appear as'th-e description proceeds.

According to the invention figured cellulosic textiles are providedwhich com'prise'defined areas of permanent transparence and defined areas of a nontransparent character, the fibres within the latter areas being pigmented with the aid of a hydrophobic substance of a fatty character con taining coloring pigments. ,j By the terms hydrofects on loose, broad looped textile surfaces are obtained by printingfthem with-a solution con,- taining pigment and/or cellulose :or instead of the cellulose, albumine or resins a'ndItoi parchmentise the fabric after the fixation o'ffthe' resist layer produced by the printing. vParticularly the use of carbarnide-forrnaldehyde. condensates, as dimethylolcarbamid and melamine-formaldehyde-condensates, phenol-formaldehyde-condensates and polymerisates, e. g. polystyrol 'asbinding materials has been utilized for obtaining figured effects by pigment printing; in combination with a subsequent parchmentizing process. ,Wi th such aprocess, the eventual addition of plastifyin-g agents to condensates of anaminoderivate of triazine with an aldehydehasbeen suggested andpolive oil, glycerine, parafiine oil, and certain quaternary ammonium pompounds were mentioned as examples. The addition ofhydrophobe compounds as parafin, wax, resins and aluminum salts to such binding compounds has been considered but the binding of the pigments has been obtained in such compositions by the use; of artificial resins, the. hardness and stiffness of which has been reduced by such additions.

, This invention aims at providing cellulosic textile goods for instance cotton fabrics, such-as organdie, in whichcertain-defined areas are of ,permanent transparence and'other defined areas, are non transparent, the non transparent areas being pigmented without imparting to the textilelgoods an additional stiffening 'at the non transparent parts. Another object of this invention is to provide such textile goods having a clear pattern of great lucidity and'beauty and inwhich each phobic substance of a fatty character I include such substances which have the physical qualities of fats, that is to say oleaginous substances which exercise a repellent action against wate and aqueous solutions, but are capable of being emulsified, and which are capable of forming smooth and non-cracking deposits or films on a base on which they are applied; Examples of such substances of fatty character are higher'hydro carbons, particularly paraffin, glycerides, for eX'-" ample animal or vegetableoils a'nd'fats, waxes and higher fatty acids, commonly occurring in natural fats and oils or mixtures thereof.

For producin figured textiles for instance woven or knitted fabrics or yarns; especially from native cellulose, according tothe invention the fabrics are printed in pattern withprinti'ng pastes, 1

which contain pigments and/ or compounds which form pigments by hydro-lysis'or thermal'decomposition, and besides auxiliary printing agents re-'- movable by washing, and oleaginous substances such as hydrocarbons, glycerides, waxes, higher fatty acids or their salts or a mixture of these substances in the form of an emulsion, these'substances being per'sehydrophobic or forming hydrophobic substances when treated by concentrated acids. The'printe'd textiles are then dried and/or steamed and treated with concentrated acid, preferably sulphuric acid of more than 40? f B., or agents reacting inthe same way forebtaimng a permanent fixation of the pigments.

Printing pastes comprising emulsions of paraf fin or cerine or beeswax, or of tallow, stearine',

stearine soaps or wax soaps, to which have been 1 added emulgents, protectivecolloids, rpther, ad

'ditional and auxiliary compounds mayjb-e used according tgtheinven'tion'. Such oleaginous'substances may also be, made ,einulsive Water by sulphonation or p'artialsiilphonation, If salt of fattyacids (soaps) aref usd as' the fatty compastes.

Prefabricated pigments maybe added to the printing pastes used according to the invention or, the same result may be accomplished by utilizing metal salts, which by hydrolysis or thermal decomposition under the conditions'of the process form insoluble precipitates which serve as the pigment substance. Such salts may also be used, which at the same time electrically charge or reverse the electrical charge of the emulsion to -the positive.

surpris'inigly, it has been proved, that the em ulsions, -whicha1e'freo 1ientlynot completely cpagula ted," when brought'on the fibre and'subsium-tartrate, lead chloride, bismuth carbonate, stannates of alkalin, zinc acetate, or magnesium chloride are used. The precipitates, originated from these metal salt solutions during the treatment are resistant against washing and boi1- ing'; v

It is useful to add cation active compounds to the printing paste, like lauryl pyridinium sulphate, which are able to charge or to: recharge the pastes electrically, or to use a pigment suspension, obtained from such cation active compounds,- in'the printing paste. To adjust the printing qualities of the printing paste, additional and auxiliary compounds conventionally used in cloth printing and which are removable bywashing are added, singly or in a mixture, as diluting, thickening, plastifying, softening or stiffening agents or agglutinants. Also filling, lustre making, dull making, metallising, corroding, luminescent or dyeing compounds may be added to the printing paste.

It is remarkable, thatusually only a comparatively small percentage of hydrophobic emulsifled compounds in the printing paste is suflicient to produce the results aimed at by the invention, as will be apparent from the hereinafter described processes and examples which sequ tly dried and eventually steamed, eoagu ing am iepei at a subsequent treatment with acid, -f or instance concentrated sulphuric acid of more than approximately 40 B., preferably" to B., as use'd'forproducing translucent effects transparentis'ing' v and parchmentsinger producing'linendike effects, or withother simila'fly'a'cting swelling agents; By this, the insqliib'l ,c ompo 'ndsoruie printing paste are very stably'fixed on and inthefib're. Upon this tre'at- V fliers, with acid, a very strong bonding between the'hydiophobic precipitate and'thefibre is established. This" binding action may result from electrical {reverses and discharges between the fibre, the emulsion'colloids or the product of the coagulation, the metal salt and the concentrated acid. A's'a result, a part of the pigments added to the printing pasteiss'urroun'ded by the precipitated'compounds and fixed on the fibre in a manner'whicliis surprisinglyresistant against rubbing, washing and boiling. The unbound surplusjoi the pigments is preferably removedby washing before thetextiles are treated on frames and ,ifiriished. The treatment of the printed fabrics with acids is effected without shrinkin byflern'ploying' simultaneous or subsequent tension; thereby producing a surface pattern on the fabric. 1 ;Examples of various prefabricated pigments, which may be incorporated into the printing paste are: titanium dioxide, zinc white, permane'nt white, kaolin,lithopone, colloidal silicic acid, and other equivalent" mineral pigment'substances. Instead of the prefabricated pigments, or in addition" thereto, solutions of metal salts may be added to the printing paste which yield pig'- mentsasa' result of the drying or steaming step by a hydrolysis or thermal decomposition, leading'toaprecipitation of white, insoluble oxides on the fibre whichjmake the fibre dull and which are resistant against washing. Solutions of basic "salts of similar qualities" may also be used. For thi's'purpose, preferably non-'cor'roding alumini'uiii-,fantiiiiony-,bismuth-, tin, lead-, zinc, and

set forth representative compositions'of a printing paste formulated according to the invention.

The process according to the invention maybe used for obtaining patterns on cotton textiles. The textiles to be subjected to the process according to the invention may be in a raw state or partially refined, e. g. bleached, mercerised, dyed, calendered or in any other way pretreated oriretreate'd, either as toa part of the yarns or completely. The textiles may be of various density and weave and may contain yarns of equal or unequal quality or strength and twisting or overtwisting. I

This process may also be combined with one of the known refining processes, as for instance an impregnation or an anticrumbling treatment, for instance with artificial resins such as dimethylcarbamide, or a finishing process, for in stance with cellulose others. It may also be combined with an esterification or alkoxylation or with-the usualpigment' printing or color printtiles may also be dyed before or after the producmagnesium salts, as aluminium acetate, alumintion of the pattern process.

All variations of printing effects, which may be realizedaccording to the process of the inventionm'ay be produced by one or more stages either singly or in parallel, either partly or completelycovering each other, with or without white and/or colored effects, with or without a local or "complete swelling process.

A n-irnportant way of realizing the proces'saccording to the invention, is to combine it with swelling processes of Various kinds, wherein the local printing with the printing paste according to theinventi'onmay be 'efiected before, or betweentwo'or more, or after the swelling processes.

'rfowever, it'is necessary in anycase to fix the pigments after the printing and the subsequent steaming or drying 'b-ythe treatment with con- 'centrated' sulphuric acid'or" similar agents; Thus the fabrics may be mercerized before the printing, o'rfthe printed fabrics may be merceri'zed after the treatment with acids, or they maybe subjected to both treatments; 'By the swelling processes various effects, for instance wool like ing .process with transparentizing agents.

effects, linenor silk-like effects or opalescent,

parchmentized, or transparent or similar effects may be obtained, as are well known, by different working conditions (type and concentration, temperature, time of reaction of the swelling agent,

addition of preservative compounds to the swelling agent, stretching of the fibre and the surface during the treatment, local reaction or reaction on the whole surface, direct printing or reserve printing, combined with a swelling process on the whole surfacaproducing a single or parallel or partly or completely covering pattern).

The products obtained by the process according to the invention show a very considerable difference compared to the known figured fabrics, the advantages being particularly apparent when employed in connection with loose fabrics having broad loops, since themanner of the local covering of the threads with this process is essentially different than that accomplished by any heretofore known. With the process according 'to the invention only the single threads in the parts printed with the pattern are covered, while the spaces between the threads are not filled. The same effect is secured in the printed parts of a cotton muslin fabric for instance, each thread remaining visible, while the unfixed printing paste between the threads is removed by washing.

After passing the printed fabric through a bath of sulphuric acid or other transparentizing agent the comparatively small amount of insoluble hydrophobic compounds is precipitated on and in the fibre, which after the removal of the surplus of emulsion and pigments forms a pattern of great lucidity and beauty and which possesses a great resistance against soap, boiling, rubbing and light. The prints produced in accordance with the invention do not tend to dust off, as happens frequently when the usual pigment binding agents are used and which in the case of patterns with a large surface, cover or fill a part of the space between the threads of the fabric. The textiles figured by the process according to the invention also show an outstanding equality and homogeneity of the print. The parts figured with pigments also have a softer quality than the transparent parts and a flexible touch, which aplinenware. The products produced by the subject invention compare favorably with products obtained by the much more diflicult direct print- The -pears advantageously with pigment patterns on certain products, as handkerchiefs, curtains and resistance of the patterns against light also offers common products in commerce for the porous hydrophobic impregnation of textiles and may be utilized in preparing the described printing pastes.

Examples (1) A cotton muslin, bleached and mercerized with alkali in the usual way is printed in accordance with a pattern-with a printing paste of the following composition:

6 400 g. thickening agent: wheat starch, tragacanth 6%, Water in a relation 1 2 5. 100 g. of an aqueous emulsion of paraffin g. filtered water-glass 38 B. (colloidal silicate) 200 g. titanium dioxyde 1:1

50 g. glycerine 160 g. water 1 1O cm. indanthrene blue 2% (Schulz Farbstofi'tabellen, 2 supplement 1939, page 199,

Indanthrenblau R. Z.)

The printed fabric is then dried, steamed wet, parchmentised under tension in concentrated sulphuric acid of 54 B. at a temperature of 2 C.

for 8 to 13 seconds, then neutralised or washed, then treated with sodium lye of 27 B. for 20 seconds, neutralised again and rinsed. By a subsequent frequent washing, whichmay be continued up to the temperature of boiling water, the surplus of pigments is removed and after a test showing the absence of pigments in the rinsingv water, the fabric is eventually dressed, then treated on frames and finished. White, dull contrast patterns on a transparent ground are obtained.

(2) After the same preliminary treatment, a cotton fabric is printed with:

Instead of g. of said aqueous emulsion of tallow, 100 g. of an emulsion of any hydrophobic substance previously specified compounds with zirconium oxychlorideor zirconium oxynitrate or hydrolysates of these salts may also be used. The subsequent treatment is the same as in Example 1. White dull printing effects on a transparent ground are obtained. If a fabric dyed with indanthrene or indigosole colors is printed with this printing paste and then treated in the indicated way, white contrasts, resistant against light and washing, on a transparent colored ground are obtained.

(3) After the same preliminary treatment, a cotton muslin fabric is printed with:

450 g. thickening agentz' wheat starch, tragacanth 6%, water in a relation of 1:225

g. an aqueous emulsion of 'paraffi'n containing soluble aluminium salts 50 g. aluminium acetate 8 200 g. titanium dioxyde 1:1

50 g. glycerine 10 g. indanthrene blue 2% (Schulz Farbstofftabellen, 2' supplement 1939, page 199, IndanthrenblauR. Z.)

100 cm. water This product is dried, steamed wet at a temperature of more than 100 C.and then treated the same iwayas in Example 1; Oneobtains white, contrasting reserve patterns on a 'transparent ground. If the transparent product which is printed with white effects is dyed with substantive dyes, as sirius light blue,:the result is effects of one tinge passing into theother.

(4) A cotton muslin fabric, bleached and mercerised in the usual way is printed with the following paste:

550 g. thickening agentz wheat starch, tragacanth 6%, water in a relation of 1:2:5

200 g. titanium dioxyde 1:1

85 g.1.of an aqueous emulsion of parafiin congtaining soluble'aluminium salts 35 g. weaklysulfonated tallow' 50 g. glycerine g. indanthrene blue (Schulz Farbstofitabellen, 2 supplement 1939, page 199, Indanthrenblau R. Z.) 2%.

This paste is added to the following composition: v

38 g. thickening agent: wheat starch, tragacanth 6%, British gum, water, in a relationof 1:3:5

'g. water 3 g. Indanthrene blue (Schulz Farbstoiitabellen, 2 supplement 1939, page 199, Indanthrenblau R. Z.)

35 g. wheat starch 45 g. water '75 g. tragacanth 6% g. British gum solid 45 g. glycerine 60 g. potassium carbonate 40 g. rongalite (NaI-ISOaCI-IzQZHzO) 10 g. turpentine oil g. water Afterthe printing process, the :textiles.- are dried and steamed :in 'the rapid-steaming: sap?" paratus and. transparentised and subsequently? treated in the usualjway; The result is ashining"v blue contrast print on a -transparent grounds The composition I-mayalso be used for obtaining white prints. i

(5) A cotton muslin is bleached,;z nercerised and dyed light blue with a substantive dye which;

may be-disch'ar'ged in vneutral,solution.and then printed with:

After drying and steaming for 5 minutes in the rapid-steaming apparatus, the-producti's' trans;

8 The'result is a plastic white ,contrastpattern on a light, blue ground.

I claim 1'. A process for producingjipatterns on a-cotton'textilecomprising the steps of printingapattern on the textile:withacomposition comprisingan' acidstable mineral pigment and an aqueous emulsion of an voleaginous substance; the oleaginous substance being'the'sole pigment binding agent present, drying the printed textile, and

thereafter :treating .the printed textile with an acid transparentizingiagent, whereby the non-,

printed portion of the textile is transparentized and the pigment is bonded to the printed portionthereof, and thereafter washing the textile to remove the unboundsurplus of pigment.

2. Aprocess forproducing figured cotton textile goods comprising .the steps of. printing a pattern ontthegoods with-a printing paste comprising an' aqueous emulsion of an oleaginous substance, athickening agent, and an acid stable mineral coloring substance, the oleaginous substance being the. sole :pigment binding agent present, drying the printed goods, and thereafter treating the goods with artransparentizing agent for the purpose of transparentizing the nonprinted areas and bonding. said coloring substance tothe fibers defining the printed areas of the goods;

3; A process for producing a figured cotton textile which comprises the steps of printing apate tern'on defined areas of the textile with'a composition comprising an acid stable mineral pigment and an aqueous emulsion of 'parafiin, the parafiin" being. the sole pigment binding: agent present, drying the printedrtextile, and treating the :dried textile with anacid transparentizingagent.

4. A'process forproducinga figured cotton textile which comprises thessteps of printinga pattern undefined areas-of the textile with a com= position comprising an acid stable-mineral pigment and an aqueous emulsion of parafiin, the paraflinbeing the sole pigment binding agent present; drying the I printed textile,- steaming it wet, treating the :dried textile with concentrated sulphuric acid, whereby the non-printed areas are transparentized and the-pigment is bonded to the fibersin the printed areas, and thereafter washing the textile to removethe unbound surplus of pigment. I

5 -A-process for-producinga figured cotton textile-which comprises the steps of printingapatternpn defined -areasot the textile with a composition'comprisingian acid stable -mineral-pigposition =comprising an acid stablemineralpigment and an aque'ous' emulsion of an oleaginous substance, the olea'ginous substance being the sole pigment binding agent present, drying the printed textile, steaming it wet,-treating the dried textile with concentrated sulphuric acid, whereby'thenon printed areas are'transparentized and the pigmenti's bonded to the fibers "in the printed" v areas, and thereafter washing the textile'to're parentised and-finished 'lIY'tl'lB' described "way." 'more the unbound surplus'of pigment.

9 7. A cotton textile product obtained by the,

Number process claimed in claim 1. 2,171,513 HEINZ GINZEL. 2,174,534 2,202,200 REFERENCES CITED 2,275,991 The following references are of record in the 2,298,147 file of this patent:

UNITED STATES PATENTS Number Name 1 I Date 10 Number 2,000,509 Schoen May 18, 1937 413,150

Name Date Heberlein et al. Aug. 29, 1939 Shlpp Oct. 3, 1939 Heller et a1 May 28, 1940 Powers Mar. 10, 1942 Miller Oct. 6, 1942 FOREIGN PATENTS Country Date Great Britain July 12, 19 34 

1. A PROCESS FOR PRODUCING PATTERNS ON A COTTON TEXTILE COMPRISING THE STEPS OF PRINTING A PATTERN ON THE TEXTILE WITH A COMPOSITION COMPRISIN AN ACID STABLE MINERAL PIGMENT AND AN AQUEOUS EMULSION OF AN OLEAGINOUS SUBSTANCE, THE OLEAGINOUS SUBSTANCE BEING THE SOLE PIGMENT BINDING AGENT PRESENT, DRYING THE PRINTED TEXTILE, AND THEREAFTER TREATING THE PRINTED TEXTILE WITH AN ACID TRANSPARENTIZING AGENT, WHEREBY THE NONPRINTED PORTION OF THE TEXTILE IS TRANSPARENTIZED AND THE PIGMENT IS BONDED TO THE PRINTED PORTION THEREOF, AND THEREAFTER WASHING THE TEXTILE TO REMOVE THE UNBOUND SURPLUS OF PIGMENT. 